U.S. patent number 5,064,799 [Application Number 07/637,407] was granted by the patent office on 1991-11-12 for components and catalysts for the polymerization of olefins.
This patent grant is currently assigned to Himont Incorporated. Invention is credited to Antonio Monte, Luciano Noristi.
United States Patent |
5,064,799 |
Monte , et al. |
November 12, 1991 |
Components and catalysts for the polymerization of olefins
Abstract
Disclosed are catalyst components for the polymerization of
olefins comprising the product of the reaction of a tetravalent
titanium halide or alkoxy titanium halide and an electron-donor
compound with a solid obtained by the reaction of a metal oxide
containing surface hydroxyls, preferably together with chemically
uncombined water, with an organometallic magnesium compound used in
a quantity which does not cause reduction of the titanium in the
subsequent reaction with the tetravalent titanium compound.
Inventors: |
Monte; Antonio (Ferrara,
IT), Noristi; Luciano (Ferrara, IT) |
Assignee: |
Himont Incorporated
(Wilmington, DE)
|
Family
ID: |
11153964 |
Appl.
No.: |
07/637,407 |
Filed: |
January 4, 1991 |
Foreign Application Priority Data
|
|
|
|
|
Jan 10, 1990 [IT] |
|
|
19030 A/90 |
|
Current U.S.
Class: |
502/115; 502/116;
502/126; 526/124.8; 526/124.6; 526/129; 502/120; 502/127 |
Current CPC
Class: |
C08F
10/00 (20130101); C08F 10/00 (20130101); C08F
4/6545 (20130101); C08F 10/00 (20130101); C08F
4/6543 (20130101); C08F 10/00 (20130101); C08F
4/651 (20130101) |
Current International
Class: |
C08F
10/00 (20060101); C08F 004/651 () |
Field of
Search: |
;502/115,116,120,126,127 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
4263168 |
April 1981 |
Rochefort et al. |
4971937 |
November 1990 |
Albizatti et al. |
|
Primary Examiner: Garvin; Patrick P.
Claims
We claim:
1. A solid catalyst component for the polymerization of olefins
comprising the reaction product of a tetravalent titanium halide or
alkoxy titanium halide and an electron-donor compound with a solid
obtained by reacting a metal oxide containing surface hydroxyl
groups, with an organometallic magnesium compound of the
formula:
where R is a C.sub.1-20 alkyl, C.sub.3-20 cycloalkyl, C.sub.6-20
aryl, C.sub.7-20 aralkyl or alkaryl radical; X is a halogen, OR or
COX' radical where R is as previously defined, X' is a halogen and
x is a number from 0.5 to 1.5, wherein at least 80% of the titanium
which is present in said catalyst component is in the tetravalent
state.
2. The catalyst component of claim 1, wherein the metal oxide is
selected among from the group consisting of silica, silica-alumina
mixed oxides containing minor amounts of alumina, alumina and
magnesium oxide.
3. The catalyst component is claim 1, where the oxide contains from
1 to 3 mmoles of hydroxyl groups per gram of oxide.
4. The component of claim 1, wherein the oxide contains up to 15
mmoles of chemically uncombined water per gram of oxide.
5. The catalyst component of claim 1, wherein the total amount of
magnesium compound, titanium compound and electron-donor compound
is from 5 to 60% by weight, the Mg/Ti molar ratio is from 0.5 to 8,
and the molar ratio of the electron-donor compound /Mg is from 0.05
to 0.2.
6. The catalyst component of claim 1, wherein the titanium halide
is titanium tetrachloride, the electron-donor compound is selected
from ethers having the formula ##STR2## where R, R.sub.1, and
R.sub.2, are the same or different and are linear or branched are
C.sub.1-18 alkyl, C.sub.3-18 cycloalkyl, C.sub.6-18 aryl, or
C.sub.7-18 alkaryl or aralkyl radicals, and R.sub.1 or R.sub.2 can
also be hydrogen.
7. The catalyst component of claim 1, wherein the electrondonor
compound is a phthalic acid ester.
8. The catalyst component of claim 1, where the organometallic
magnesium compound is alkylphenyl magnesium chloride or
bromide.
9. A catalyst for the polymerization of CH.sub.2 .dbd.CHR olefins,
wherein R is a 1-6 carbon linear or branched alkyl radical or an
aryl radical, comprising the reaction product of the solid catalyst
component of claim 1 with an Al-trialkyl compound.
10. The catalyst for the polymerization of olefins of claim 9
comprising the reaction product of the solid catalyst component of
claim 7 with an Al-trialkyl compound and a silicon compound
containing at least one Si--OR bond where R is a hydrocarbyl
radical.
Description
The present invention concerns catalyst components for the
(co)polymerization of CH.sub.2 .dbd.CHR olefins, where R is
hydrogen or a 1-6 carbon linear or branched alkyl radical or an
aryl radical, and the catalysts obtained therefrom.
Catalysts for the polymerization of olefins obtained by
impregnating a metal oxide containing surface hydroxyls, such as
silica and alumina, with an organometallic compound, preferably an
Al-trialkyl or Mg-dialkyl compound, used in molar excess with
respect to the surface hydroxyls, and subsequently reacting the
support with titanium tetrachloride are known (GB1,256,851 and
1,306,044). The catalysts are suited for the polymerization of
ethylene; however, they do not give sufficiently high yields
(300-500 g polymer/g catalyst component per hour and operating with
an ethylene pressure of 10 atm).
Should the catalysts be modified with electron-donor compounds in
order to render them stereospecific and thus suited for
stereoregular polymerization of propylene or other alpha olefins,
one can expect a considerable reduction in activity, which is
already not too high in the polymerization of ethylene.
In U.S. Pat. No. 4,263,168 catalyst components for the
polymerization of propylene and other alpha-olefins obtained by
reacting a metal oxide containing surface hydroxyls (silica,
alumina, etc.) with an organometallic magnesium compound of the
formula MgR(.sub.2-x)X.sub.x (where R is a hydrocarbyl radical; X
is a halogen; x is a number from 0.5 to 1.5), and subsequent
reaction of the oxide first with an electron-donor compound, and
then with titanium tetrachloride are disclosed. The organometallic
magnesium compound is reacted in molar excess with respect to the
hydroxyl groups, while the electron-donor compound is used in
quantities up to 1 mole per mole of reacted magnesium compound,
preferably 0.5-0.8 moles. The reaction with TiCl.sub.4 is carried
out by using an excess of TiCl.sub.4.
In one embodiment the metal oxide, either before or after the
reaction with the organometallic magnesium compound, is reacted
with a halogenating agent in such a quantity as to supply at least
one halogen atom per hydroxyl group. The halogenating agent can
also be added during the reaction with the electron-donor compound.
The activity and sterospecificity of these catalysts are not
sufficiently high, i.e. capable of rendering them attractive for
use on an industrial scale.
The high activity of the catalysts based on magnesium halides
supported on metal oxides, combined with a good stereospecificity,
not only reduce the content of undesired halogenated compounds
which remain in the polymer, but also enables to control, in a
relatively simple manner, the morphology of the polymer. In the
modern industrial production processes of polyolefins, there is a
need for catalysts capable of producing a polymer with controlled
morphologic characteristics, such as narrow particle size and
sufficiently high bulk density.
This invention provides catalyst components for the polymerization
of CH.sub.2 .dbd.CHR olefins, where R is a hydrogen, or a 1-6
carbon linear or branched alkyl radical or an aryl radical, having
very high activity and stereospecificity. Said catalyst components
comprise the reaction product of a tetravalent titanium halide or
alkoxy titanium halide and an electron-donor compound with a solid
obtained by the reaction of a metal oxide containing surface
hydroxyls, preferably together with chemically uncombined water,
with an organometallic magnesium compound of the formula:
where R is a C.sub.1-20 alkyl, C.sub.3-20 cycloalkyl, C.sub.6-20
aryl, C.sub.7-20 aralkyl or alkaryl radical, X is a halogen, OR or
COX' group where R is as previously defined, X' is halogen, x is a
number from 0.5 to 1.5, used in quantities and under conditions
such as not to cause reduction of the titanium during the reaction
with the tetravalent titanium compound. Suitable halogens include
chlorine and bromine.
The amount of organometallic magnesium compound which under the
reaction conditions indicated below, does not cause reduction of
the tetravalent titanium compound, is equal to the stoichiometric
quantity (1 mole) of magnesium compound per OH group or per mole of
water or higher. In the case of magnesium compounds such as methyl
magnesium chloride or bromide dissolved in diethyl ether or
tetrahydrofuran it is possible to use up to about 2 moles of
magnesium compound. In the case of compounds, such as butyl,
isoamyl, n-octyl magnesium chloride or bromide it is possible to
use up to 10 moles per mole of OH groups or of water.
The expression "no reduction of titanium" means that at least 80%
of the titanium present in the solid after the reaction with
titanium tetrachloride and with the electron-donor compound is in
the tetravalent state.
Operating under conditions where there is a reduction of the
titanium, using, for example, an excess of organometallic magnesium
compound, the activity and stereospecificity of the catalyst are
considerably reduced. It is unexpected that the catalysts of this
invention would have high activity and stereospecificity eve when
the metal oxides contain chemically uncombined water. In fact water
is rigorously excluded from the oxides in the processes used up to
now for the preparation of olefin polymerization catalysts which
use said oxides. Another unexpected aspect of the catalysts of this
invention is the fact that they are very active in the
polymerization of propylene and similar alpha-olefins, but not in
the polymerization of ethylene.
The metal oxides which can be used for the preparation of the
catalyst components include silica, alumina, magnesium oxide and
magnesium silicate, titanium oxide, thorium oxide, mixed
silica-alumina oxides containing minor amounts of alumina. Silica,
alumina, and mixed silica-alumina oxides are the preferred oxides.
Said oxides contain surface hydroxyls in an amount of from 1 to 3
mmoles, and more, per g of oxide. Preferably, in addition to the
hydroxyl groups, chemically uncombined water is also present in
quantities up to 0.015 moles per g of oxide. The oxides generally
have a surface area (BET) higher than 30 m.sup.2 /g, particularly
between 100 and 500 m.sup.2 /g, and porosity (measured with
nitrogen) from 0.5 to 3.5 cc/g.
The chemically uncombined water can be removed by submitting the
oxides to heat at temperatures between 150.degree. and 250.degree.
C.
The quantity of OH groups is regulated by submitting the oxides to
heat at temperatures between 150.degree. and 800.degree. C. The
higher the temperature, the smaller the content of hydroxyl groups
present.
The chemically uncombined water is added in a variety of ways; one
of the preferred ones consists in allowing a damp nitrogen current
to flow over the oxide. Optionally the oxide may be previously
treated to render it anhydrous.
The amount of OH groups is preferably from 1 to 3 moles per gram of
oxide and the water, when present, is preferably in amount from 1
to 10 mmoles per gram of oxide.
The amount of OH groups present in the metal oxide is determined by
titration according to the method described in J. Phys. Chem., 66,
800 (1962), and the amount of water present with the Fisher
reagent.
The magnesium organometallic compound can be used uncomplexed or in
the form of a complex with electron-donor compounds, such as
ethers, particularly diethyl ether and tetrahydrofuran.
In general the quantity of complexing agent complexed with the
magnesium compound is from 0.5 to 3 moles, and preferably from 0.5
to 1 mole per mole of magnesium compound.
Examples of magnesium organometallic compounds are: methylmagnesium
chloride, methylmagnesium bromide, n-butylmagnesium chloride,
isobutylmagnesium chloride, isoamylmagnesium chloride,
n-octylmagnesium chloride, n-propylmagnesium bromide,
n-butylmagnesium ethoxide and ethylmagnesium methoxide.
The reaction between the metal oxide and the magnesium
organometallic compound is carried out at temperatures generally
from 0.degree. C. to 100.degree. C. in an inert hydrocarbon medium.
After the reaction is completed, the solid is preferably separated
and washed with hexane, heptane, or other similar hydrocarbons.
However, it is possible to also use the resulting suspension
without separating the solid.
The preferred technique is to add the magnesium organometallic
compound solution dropwise to a suspension of the metal oxide in
hexane, heptane, and similar hydrocarbons.
After the treatment with the magnesium organometallic compound, the
metal oxide is reacted with the tetravalent titanium compound and
the electron-donor compound. Preferably the titanium compound is
titanium tetrachloride, and the reaction is carried out using the
tetrachloride itself as the reaction medium. The reaction is
carried out at a temperature between 40.degree. and 135.degree. C.
for a period from 0.25 to 1 hour or more. After the reaction is
complete the excess TiCl.sub.4 is separated hot and the solid is
washed repeatedly with a hydrocarbon hexane until all chlorine ions
have disappeared from the wash. It is preferred to repeat the
treatment with TiCl.sub.4 one or more times, and the solid washed
as indicated above.
The reaction with the electron-donor compound is carried out at the
same time as the one with the titanium compound. In the case of
TiCl.sub.4, the electron-donor compound is dissolved in the
TiCl.sub.4 excess, and the solution is reacted with the metal
oxide. The amount of electron-donor compound is between 0.1 and 1.5
moles per g-atom of Mg, preferably between 0.2 and 0.4 moles.
The electron-donor compound can also be reacted before or after the
reaction with the titanium compound. When it is reacted after, the
reaction should be carried out in an aromatic hydrocarbon medium,
such as benzene and toluene, using equimolar amounts of
electron-donor compound with respect to the titanium compound fixed
on the metal oxide.
The best results are obtained, however, by reacting the
electron-donor compound before or at the same time as the titanium
compound.
Any electron-donor compound capable of forming complexes with the
magnesium halides and/or the tetravalent titanium halides can be
used for the preparation of the catalyst component of this
invention. Examples of compounds that can be used are the ethers,
esters, ketones, lactones or compounds containing N, P and/or S
atoms. Preferred compounds are the esters of dicarboxyl aromatic
acids, such as phthalic acid, and the esters of malonic, pivalic,
succinic, and carbonic acids. Particularly suitable are the ethers
described in U.S. Pat. No. 4,971,937 having the formula: ##STR1##
where R, R.sub.1, and R.sub.2, are the same or different and are
linear or branched C.sub.1-18 alkyl groups, C.sub.3-18 cycloalkyl
or C.sub.6-18 aryl groups, C.sub.7-18 alkaryls or aralkyls, and
R.sub.1 or R.sub.2 can also be hydrogen. Particularly, R is a
methyl and R.sub.1 and R.sub.2, are the same or different and are
ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl,
isopentyl, phenyl, benzyl, or cyclohexyl.
Specific ethers are diisobutyl, dioctyl and diphenylphthalate,
benzyl-butylphthalate, diisobutyl and diethylmalonate,
ethylpivalate, ethyl-phenylcarbonate, diphenylcarbonate.
Representative ethers are 2,2-diisobutyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,
2,2-bis(cyclohexyl)-1,3-dimethoxypropane.
After the treatment with the magnesium compound the metal oxides
have a Mg content is from 0.5 to 20% by weight and, the solid
catalyst components have a Mg/Ti molar ratio of from 0.5 to 8.
The electron-donor compound is generally present in quantities from
5 to 20%, and in particular from 10 to 15% in moles per g-atoms of
magnesium. The total quantity of magnesium halide, titanium halide
or alkoxy titanium halide, and electron-donor compound present in
the solid catalyst component is from about 5 to 60% by weight.
The surface area (B.E.T.) of the solid catalyst component is
generally greater than 100 m.sup.2 /g, preferably from 100 to 300
m.sup.2 /g.
The solid catalyst components form, with Al-alkyl compounds,
preferably Al-trialkyls, catalysts suitable for the polymerization
of CH.sub.2 .dbd.CHR olefins where R is hydrogen, a 1-6 carbon
linear or branched alkyl radical or an aryl radical, and mixtures
thereof optionally containing small proportions of a diene.
Representative Al-trialkyl compounds are Al-triethyl,
Al-triisobutyl, Al-tri-n-butyl, and linear or cyclic compounds
containing two or more Al atoms bridged with O or N atoms, or
SO.sub.4 and SO.sub.3 groups.
AlR.sub.2 OR' and AlR.sub.2 H compounds where R' is an aryl radical
substituted in position 2 and/or 6 with alkyl radicals, preferably
branched, having three or more carbon atoms, such as isopropyl,
t-butyl, isoamyl and neopentyl, and R is a 1-6 carbon alkyl
radical, and AlR.sub.2 H compounds can also be used.
The Al-alkyl compound is used at an Al/Ti ratio generally from 1 to
1000.
In many cases, in order to improve the stereospecificity of the
catalyst, it is preferred to use, together with the Al-alkyl
compound, an electron-donor compound in quantities of from about
0.01 to 0.25 moles per mole of Al-alkyl compound.
The electron-donor compound is selected preferably from the ethers,
esters, silicon compounds containing at least one SiOR bound (R is
a hydrocarbyl radical), and 2,2,6,6-tetramethylpiperidine.
When the solid catalyst component comprises an ester of an aromatic
bicarboxylic acid such as phthalic acid, or an ester of malonic,
maleic, pivalic, succinic, or carbonic acid, the electron-donor to
be used together with Al-alkyl compound is selected preferably from
the silicon compounds containing at least one SiOR bond. Examples
of said compounds are phenyltriethoxysilane,
diphenyldimethoxysilane, dicyclopentyldimethoxysilane,
methyl-tert-butyldimethyoxysilane,
methylcyclohexyldimethoxysilane.
When an ether selected among those described in published European
patent application 361,494 is present in the catalyst component,
the stereospecificity of the catalyst is sufficiently high, so that
it is not necessary to use an electron-donor compound together with
the Al-alkyl compound.
The polymerization of the olefins is carried out according to known
methods operating in liquid phase in liquid monomer, or in a
solution of the monomer in inert hydrocarbon solvent, or in gaseous
phase, or also combining polymerization stages in liquid and
gaseous phase.
The polymerization temperature is generally from 0.degree. to
150.degree. C., preferably from 60.degree. to 100.degree. C. The
pressure is atmospheric or higher.
The catalysts are used both in homopolymerization and
copolymerization of olefins. In the case of copolymers, they are
used for the preparation, for example, of random crystalline
copolymers of propylene with lower contents of ethylene and
optionally of butene and similar higher alphaolefins, or of
elastomeric copolymers of ethylene with propylene optionally
containing minor amounts, i.e. 1 to 10 wt. %, preferably 3-8%, of a
diene (such as butadiene and hexadiene-1,4).
The catalysts can also be used in the sequential polymerization of
propylene and of mixtures of propylene and ethylene, and/or with
butene and similar higher alpha-olefins to form impact grade
polypropylene.
It has been found, and this constitutes a particular aspect of the
invention, that the catalysts obtained from components containing
ethers selected from those described in U.S. Pat. No. 4,971,937 are
particularly suitable to form amorphous copolymers of ethylene with
propylene optionally containing lower contents of a diene.
Before polymerization, the catalysts can be precontacted with small
quantities of olefins (prepolymerization) operating either in
suspension in a hydrocarbon solvent (hexane, heptane, etc.) and
polymerizing at temperatures between room temperature and
60.degree. C., thus producing a quantity of polymer between 0.5-3
times the weight of the solid catalyst component, or operating in
liquid monomer thus producing a quantity of polymer up to 1000 g
per g of solid component.
The following examples are given in order to illustrate the
invention.
EXAMPLES
Example 1
Synthesis of the solid catalyst component
5 g of Grace Davison 952 silica with surface area of 290 m.sup.2
/g, porosity (measured with nitrogen) of 1.53 cc/g, H.sub.2 O 4.3%
by weight measured by the K. Fischer method, are introduced in a
0.350 l reactor equipped with a filtering baffle and bottom
discharge, together with 40 ml hexane. While maintaining the
suspension with agitation, 12 ml of a 3 molar solution of MeMgBr in
ethyl ether is fed dropwise (in about 40 minutes). The suspension
is then refluxed for 1 hour. It is cooled room temperature and
filtered, after which the solid is washed 5 times with 120 ml
aliquots of hexane. It is filtered again and the solid is dried
under a nitrogen flow at 70.degree. C. for 1.5 hours. The
composition of the solid thus obtained is reported in Table 1A.
5 g of the solid component are introduced in the same reactor used
previously. 200 ml of TiCl.sub.4 are fed at room temperature and,
while agitating, the temperature is brought quickly to 70.degree.
C., after which 2-isopropyl-2-isopentyl1,3-dimethoxypropane (DMP)
is fed in such a quantity as to have a 1:3 molar ratio with respect
to the Mg contained in the catalyst component.
The temperature is brought to 100.degree. C. and the contents are
heated for 2 hours. The reaction mixture is then filtered, the
solid is returned to the reaction and 200 ml of TiCl.sub.4 are
introduced. The contents are heated at 100.degree. C. for 2 hours.
After having removed the TiCl.sub.4 by filtration, the solid is
washed with hexane, twice at 600.degree. C. and 3 times at room
temperature, then it is dried as indicated above. The composition
of the catalyst component is reported in Table 1A.
Polymerization of propylene
Into a 4 l autoclave, equipped with thermostat and agitation system
are introduced, at 30.degree. C. in light propylene flow, 75 ml of
hexane containing 7 mmoles of Al-triethyl and the quantity of
catalyst component indicated in Table 1B previously precontacted
for about 5 minutes. The autoclave is closed at 1.6 Nl of hydrogen
are introduced. While agitating, 1.2 kg of liquid propylene are
introduced, and the temperature is brought to 70.degree. C. The
autoclave is maintained under these conditions for 2 hours, after
which the agitation is stopped and the unreacted propylene is
quickly removed. The reaction mixture is then cooled to room
temperature, the polymer is recovered and then dried in an oven at
70.degree. C. for 3 hours in N.sub.2 flow. The yield is expressed
as kg polymer/g catalyst component.
The isotactic index is measured as % of polymer insoluble in xylene
at 25.degree. C. Melt index and bulk density are determined
according to ASTM D-1238, condition L, and ASTM D-1895,
respectively. The polymerization results are reported in Table
1B.
Examples 2-5
The polymerization is carried out according to the method and
ingredients of Examples 1, except that the silica was previously
calcined for 7 hours under anhydrous N.sub.2 flow at temperatures
of 800.degree., 500.degree., 250.degree., and 150.degree. C.,
respectively. The composition of the catalyst component is reported
in Table 1A, the polymerization results in Table 1B.
Examples 6-8
The procedure and ingredients of Example 1 are used except that
silica enriched with water by treatment with a moist nitrogen flow
is used.
The results relative to the catalyst component and the
polymerization are reported, respectively, in Tables 1A and 1B.
Examples 9-10
The impregnation of the silica and the synthesis of the catalyst
are carried out as in Example 1, except that in this case the
electron-donor compound is di-isobutylphthalate and the
polymerization is carried out with Al-triethyl/DPMS
(diphenyldimethoxysilane) in a 20/l molar ratio instead of with the
Al-triethyl only. The polymerization results are reported in Table
1B.
Examples 11-13
The procedure and ingredients of Example 1 are used, except that
the Grignard compounds listed in Table 2A are used to impregnate
the silica. The polymerization result are reported in Table 2B.
Example 14 and Comparative Example 1
The procedure and ingredients of Example 1 are used except that a
defective amount (Example 14) and an excess (Comparative example 1)
of Grignard compound are used, respectively. The polymerization
results are reported in Table 2B.
Example 15
The procedure and ingredients of Example 1 are employed using a
noncalcined SiO.sub.2, except that 20 mmoles of Grignard (BuMgCl)
per g of silica is used. The data relative to the catalyst and
polymerization are reported in Tables 2A and 2B.
Examples 16-17
The procedure and ingredients of Example 1 are used, except that
high and low porosity silicas produced by PQ Corporation, types
988-1M and 850-40-5, having respectively, a surface area (BET) of
282 m.sup.2 /g and porosity of 2.75 cc/g, and area of 410 m.sup.2
/g and porosity of 1.37 cc/g are used to prepare the catalyst
component.
The polymerization results are reported in Table 2B.
Example 18
45 mg of the catalyst component prepared according to Example 1 are
used in the polymerization of ethylene with the modalities
indicated hereinbelow.
Into a 2.5 l autoclave, equipped with agitation and thermostat
systems, previously purged with N.sub.2 and then hydrogen at
50.degree. C., are introduced, at 45.degree. C., 850 ml a 0.0025M
Al-triisobutyl solution in anhydrous hexane. After which are fed,
under light H.sub.2 flow 45 mg of the catalyst component prepared
as described above suspended in 150 cc of said Al-triisobutyl
solution.
The autoclave is closed, the agitation started and the temperature
brought quickly to 75.degree. C. Then hydrogen is fed until the
pressure reaches 4.5 bar, and subsequently ethylene until a
pressure of 11.5 bar is obtained.
These conditions are maintained for 3 hours replenishing
continuously the consumed ethylene. When the reaction is complete,
the autoclave is vented and is cooled to room temperature.
The polymer is recovered by filtration and then dried at 70.degree.
C. for 3 hours under nitrogen flow.
The results of the polymerization are reported in Table 2B.
Examples 19-20
Into the autoclave of Example 1, previously purged with gaseous
propane flow at 70.degree. C. for 40 minutes and then cooled to
30.degree. C., are introduced, under propane gas flow, 10 cc of
anhydrous hexane containing 0.96 g of Al-triethyl and the specific
quantities of catalyst components (prepared according to the
procedure and ingredients of Examples 1 and 6 respectively)
indicated in Table 2B.
800 g of propane are then fed while at the same time starting the
agitator. The temperature is brought quickly to 75.degree. C., and
then are introduced, in succession, 2 atm of H.sub.2, 250 g of
butene-1 and ethylene until a pressure of 34 bar is reached.
These conditions are maintained for 2 hours replenishing
continuously consumed ethylene and butene-1 with an ethylenebutene
mixture 10/1 by weight. Upon completion of the reaction, the
reaction is quickly degassed, and cooled to room temperature. The
polymer is dried at 70.degree. C. for 4 hours N.sub.2 under
atmosphere.
The results of the polymerization are reported in Table 2B.
Example 21
Into a 1.35 l steel reactor quipped with an anchor agitator and
previously purged with a gaseous propylene flow at room
temperature, are introduced, in a propylene stream, 5 cc of hexane
containing 0.6 g of Al-triethyl and 104 mg of the catalyst
component prepared according to Example 1.
Then, a mixture made up of 22.3 g of propylene, 4.4 g of ethylene,
and 0.44 g of 1,4-hexadiene (76% of trans isomer) is introduced and
a pressure of 11 bar is obtained.
The temperature is quickly brought to 35.degree. C. and it is
maintained under these conditions for 4 hours continuously by
feeding a propylene/ethylene/1,4-hexadiene mixture in a 67/30/3
weight ratio to compensate for any pressure drop resulting from the
consumption of these monomers. Upon completion of the reaction, the
unreacted monomers are degassed, the autoclave is purged with
N.sub.2 and the polymer is recovered; the polymer is then
stabilized with 0.1% of BHT and dried under nitrogen at 60.degree.
C. for 2 hours. 135 g of polymer are obtained (yield equal to 1.3
kg of polymer/g of catalyst component) in flowable spheroidal
particles with following composition in weight % of
ethylene/propylene/hexadiene: 35.1/63/1.9.
For the determination of the mechanical characteristics, the
polymer is vulcanized (after homogenization in a calendar roll at
80.degree. C. for 10 minutes) in a plate press at 160.degree. C.
for 30 minutes with the following formulation) percentage by
weight):
______________________________________ Polymer 51.35 ZnO 2.57
Stearic acid 0.51 FEF carbon black 28.24 100 M Cortis oil 14.50
Tetramethylthiuram monosulfide 0.77 Mercaptobenzothiazole (MBT)
0.39 Sulfur 0.77 ______________________________________
The tension set at 100% is 8.4; the tensile strength (MPa) is 11.3,
and the elongation at break is 440%.
Comparative example 2
The procedure and ingredients of Example 1 are used, except that
the Mg compound is a dialkyl (BEM of Texas Alkyls). The results are
reported in Tables 2A and 2B.
Comparative Example 3
The catalyst component is prepared according to the procedure and
ingredients of example 1 except that a Davison 952 silica calcined
at 150.degree. C. for 7 hours is used and the treatment with
TiCl.sub.4 is carried out, in the absence of the electron-donor
compound.
The composition of the catalyst component is reported in Table
2A.
The component is used in a propylene polymerization test using
Al-triethyl/DPMS according to the methods of Examples 9-10.
The results of the polymerization are reported in Table 2B.
Example 22
5 g of Al.sub.2 O.sub.3 of Akzo Ketjen B (pseudobohemite
crystalline form) with surface area 266 m.sup.2 /g and porosity
0.64 cc/g (B.E.T.), and a water content (K. Fischer)=17%, are
pretreated at 100.degree. C. under vacuum (1 hour at 100 torr+1
hour at 10 torr) in order to bring the free-water content to 3.55%
(equal to 2.04 mmoles/g Al.sub.2 O.sub.3), and then impregnated
with a 3M solution of MeMgCl in THF (6 mmoles/g Al.sub.2 O.sub.3)
according to the procedure described in Example 1. Then, following
the same procedure, the treatment with TiCl.sub.4 and DMP is
carried out. The catalyst thus obtained is used for the
polymerization of propylene according to the procedure and
ingredients of Example 1 with respect to the polymerization.
Using the catalyst component thus obtained, the polymerization of
propylene is carried out according to the procedure and ingredients
of Example 1.
The results are reported in Tables 3A and 3B.
Example 23
The catalyst component is prepared according to the procedure and
ingredients of Example 22, with the difference that in this case
the Al.sub.2 O.sub.3 is first calcined for 6 hours at 800.degree.
C. (.gamma. crystalline form), then exposed to air for 5 minutes in
order to bring the free H.sub.2 O content to 4.9% (equal to 2.85
mmoles/g Al.sub.2 O.sub.3).
The results are reported in Tables 3A and 3B.
TABLE 1A
__________________________________________________________________________
PREPARATION OF THE SOLID COMPONENT Support Catalyst Component
SiO.sub.2 Mg Compound (Composition in (Composition in % by weight
Ex. H.sub.2 O --OH mmoles % by weight) Electron- No. Pretreatment
(mmol/g) (mmol/g) Type g SiO.sub.2 Mg Cl/Br Ether Ti Mg Cl/Br donor
__________________________________________________________________________
type 1 None 2.4 2.5 MeMgBr/Et.sub.2 O 7.2 9.5 --/30.8 3.8 3.75 8.4
26.5/8.8 DMP.sup.(1) 6.0 2 800.degree. C. .times. 7 h absent 0.7
MeMgBr/Et.sub.2 O 1.08 1.75 --/6.4 3.0 2.75 1.75 10/-- DMP.sup.(1)
2.0 3 500.degree. C. .times. 7 h absent 1.07 MeMgBr/Et.sub.2 O 1.54
2.9 --/9.8 3.8 4.0 2.45 15/-- DMP.sup.(1) 2.7 4 250.degree. C.
.times. 7 h absent 1.75 MeMgBr/Et.sub.2 O 1.8 3.6 --/11.9 3.3 4.4
2.95 16.5/-- DMP.sup. 2.8 5 150.degree. C. .times. 8 h 0.05 2.1
MeMgBr/Et.sub.2 O 3.6 6.6 --/23.9 4.8 4.2 6.15 23.1/4.9 DMP.sup.(1)
4.0 6 +H.sub.2 O 4.2 2.5 MeMgBr/Et.sub.2 O 8.6 11.5 --/37.0 6.5
3.85 10.65 37.3/4.8 DMP.sup.(1) 4.1 7 +H.sub.2 O 5.5 2.5
MeMgBr/Et.sub.2 O 10.3 n.d. --/n.d. 5.2 3.85 10.25 32.7/9.35
DMP.sup.(1) 4.8 8 +H.sub.2 O 8.9 2.5 MeMgBr/Et.sub.2 O 13.1 11.15
--/34.8 3.3 3.75 10.0 32.6/5.25 DMP.sup.(1) 3.9 9 None 2.4 2.5
MeMgBr/Et.sub.2 O 6.0 n.d. n.d. n.d. 4.15 6.6 29.3/-- DIBP.sup.(2)
6.8 10 800.degree. C. .times. 7 h absent 0.7 MeMgBr/Et.sub.2 O 3.0
4.55 nd/17.7 n.d. 4.35 4.1 32.5/-- DIBP.sup.(2) 8.0
__________________________________________________________________________
.sup.(1) DMP-- 2isopropyl-2-isopentyl 1,3dimethoxypropane .sup.(2)
DIBP-- diisobutylphthalate
TABLE 2A
__________________________________________________________________________
PREPARATION OF THE SOLID COMPONENT Support Catalyst Component
SiO.sub.2 Mg Compound (Composition (Composition in % by weight) Ex.
H.sub.2 O --OH mmoles in % by weight) Ti Electron- No. Pretreatment
(mmol/g) (mmol/g) Type g SiO.sub.2 Mg Cl/Br ether .sup.(1) Mg Cl/Br
donor
__________________________________________________________________________
Type 11 None 2.4 2.5 PrMgCl/Et.sub.2 O 6.0 11.6 18.5/-- 3.0 4.25
9.5 27.6/-- DMP 7.0 12 None 2.4 2.5 BuMgCl/THF 6.8 10.5 12.55/--
14.3 4.45 7.95 31.6/-- DMP 4.0 13 None 2.4 2.5 MeMgCl/THF 8.6 9.35
12.15/-- 14.2 3.9 7.5 31.8/-- DMP 4.4 14 None 2.4 2.5
MeMgBr/Et.sub.2 O 4.3 5.3 --/20.5 3.5 4.4 5.1 22.5/1.4 DMP 4.4 15
None 2.4 2.5 BuMgCl/THF 20 10.0 19.2/-- 29 4.95 9.3 36.5/-- DMP 6.2
(0.5) Comp. None 2.4 2.5 MeMgBr/Et.sub.2 O 10.8 10.0 --/31.5 5.5
4.4 9.1 23.2/18.2 DMP 3.7 1 (0.55) Comp. None 2.4 2.5 BEM 2.9 4.25
-- -- 5.05 3.1 17.4/-- DMP 1.2 2 16 None 1.64 n.d. MeMgBr/Et.sub.2
O 7.7 10 --/26.15 5.6 3.8 7.65 28/4.3 DMP 5.2 17 None 4.6 n.d.
MeMgBr/Et.sub.2 O 9.0 10.6 --/34.3 12.0 4.55 10.3 36.8/3.1 DMP 6.4
Comp. 150.degree. C. .times. 7 h 0.11 2.1 MeMgCl/THF 5.2 5.2 8.6/--
5.8 6.05 4.3 25.3/-- None -- 3 (0.4)
__________________________________________________________________________
.sup.(1) Ti.sup.3
TABLE 3A
__________________________________________________________________________
PREPARATION OF THE SOLID CATALYST COMPONENT Al.sub.2 O.sub.3
Support Catalyst Component Type of Ex. No. H.sub.2 O mmol/g OH
mmol/g MeMgCl mmol/g Mg % Cl % THF % Ti % Mg % Cl % Donor Donor
__________________________________________________________________________
22 2.04 n.d. 6.0 9.9 15.45 17.1 2.5 8.95 36.4 5.9 DMP 23 2.85 n.d.
6.7 10.3 15.1 17 2.5 9.3 34.4 6.5 DMP
__________________________________________________________________________
TABLE 1B
__________________________________________________________________________
POLYMERIZATION RESULTS Bulk Catalyst Catalyst Yield Residual Xylene
Density Example Component of Component Polymer (kg.pol/ Chlorine
Insoluble MIL (tamped) No. Example No. (mg) (g) g.cat.) (ppm) % by
weight (dg/min) (g/cc)
__________________________________________________________________________
1 1 21 555 26.4 10.2 96.1 6.6 0.435 2 2 24.5 170 7.0 13.0 97.1 4.9
0.35 3 3 21.5 240 11.2 12.0 97.3 4.2 0.43 4 4 27.5 400 14.5 9.0
97.8 5.7 0.43 5 5 19.8 440 22.2 10.3 97.0 7.4 0.44 6 6 19.8 560
28.2 12.9 94.5 8.8 0.415 7 7 18 460 25.2 11.8 94.9 14.0 0.42 8 8 21
515 24.5 13.0 94.0 n.d. n.d. 9 9 27 345 12.8 23.8 95.5 5.5 0.445 10
10 57 465 8.15 25.7 96.0 3.2 0.46
__________________________________________________________________________
TABLE 2B
__________________________________________________________________________
POLYMERIZATION RESULTS Bulk Catalyst Catalyst Yield Residual Xylene
Density Example Component of Component Polymer (kg.pol/ Chlorine
Insoluble MIL (tamped) No. Example No. (mg) (g) g.cat.) (ppm) % by
weight (dg/min) (g/cc)
__________________________________________________________________________
11 11 25.2 555 22.0 12 97.0 6.2 0.425 12 12 22.5 561 26.0 10.4 97.0
12.0 0.445 13 13 20.8 500 24.0 12.5 96.7 9.1 0.415 14 14 21.3 400
18.8 11.3 97.1 5.2 0.45 15 15 17.2 450 26.1 10.1 97.5 2.5 0.435
Comp. 1 Comp. 1 25 283 11.3 28 92.5 13 0.42 Comp. 2 Comp. 2 38 120
3.15 55 94.5 13 0.19 16 16 20.4 500 24.5 10.4 97.7 8.8 0.46 17 17
19 505 26.5 14.4 97.1 6.4 0.345 18 1 45 167 3.7 MIE--0.4 n.d. 19 1
24 250 10.4 MIE--0.22 0.9155* 20 6 20 244 12.2 MIE--0.27 0.9165*
Comp. 3 Comp. 3 25 300 12 27.5 85.2 22 0.33
__________________________________________________________________________
*Polymer density in g/cc
TABLE 3B
__________________________________________________________________________
POLYMERIZATION RESULTS Catalyst Com- PP Yield Residual chlo- Xylene
Insoluble MIL Bulk Density Example ponent mg g Kg/g rine ppm % by
weight dg/min g/cc
__________________________________________________________________________
22 20 438 21.9 14.2 96.9 6.2 0.40 23 22 476 21.6 13.6 97.0 8.2 0.40
__________________________________________________________________________
Other features, advantages and embodiments of the invention
disclosed herein will be readily apparent to those exercising
ordinary skill after reading the foregoing disclosure. In this
regard, while specific embodiments of the invention have been
described in considerable detail, variations and modifications of
these embodiments can be effected without departing from the spirit
and scope of the invention as described and claimed.
* * * * *